Process for forming an electroactive layer

ABSTRACT

There is provided a process for forming a layer of electroactive material having a substantially flat profile. The process includes: providing a workpiece having at least one active area; depositing a liquid composition including the electroactive material onto the workpiece in the active area, to form a wet layer; treating the wet layer on the workpiece at a controlled temperature in the range of −25 to 80° C. and under a vacuum in the range of 10 −6  to 1,000 Torr, for a first period of 1-100 minutes, to form a partially dried layer; heating the partially dried layer to a temperature above 100° C. for a second period of 1-50 minutes to form a dried layer.

RELATED APPLICATION

This application claims priority under 35 U.S.C. §119(e) fromProvisional Application No. 61/158,094 filed Mar. 6, 2009, which isincorporated by reference in its entirety.

BACKGROUND INFORMATION

1. Field of the Disclosure

This disclosure relates in general to a process for forming anelectroactive layer. It further relates to electronic devices having atleast one electroactive layer made by the process.

2. Description of the Related Art

An electronic device can include a liquid crystal display (“LCD”), anorganic light-emitting diode (OLED) display, a thin film transistor(TFT) array, a solar cell, or the like. The manufacture of electronicdevices may be performed using solution deposition techniques. Oneprocess of making electronic devices is to deposit organic layers over asubstrate by printing (e.g., ink-jet printing, continuous printing,etc.). In a printing process, the liquid composition being printedincludes an organic material in a solution, dispersion, emulsion, orsuspension with an organic solvent, with an aqueous solvent, or with acombination of solvents. After printing, the solvent(s) is(are)evaporated and the organic material remains to form an organic layer forthe electronic device.

There is a continuing need for deposition processes that result indevices having improved performance.

SUMMARY

There is provided a process for forming a layer of electroactivematerial. The process comprises:

providing a workpiece having at least one active area;

depositing a liquid composition comprising the electroactive materialonto the workpiece in the active area, to form a wet layer;

treating the wet layer on the workpiece at a controlled temperature inthe range of −25° C. to 80° C. and under a vacuum in the range of 10⁻⁶Torr to 1,000 Torr, for a first period of 1-100 minutes, to form apartially dried layer;

heating the partially dried layer to a temperature above 100° C. for asecond period of 1-50 minutes to form a dried layer,

wherein the dried layer has a substantially flat profile in the activearea.

There is also provided an electronic device having at least one activearea comprising an anode, a cathode, and at least one electroactivelayer therebetween, wherein the electroactive layer is formed by liquiddeposition and has a substantially flat profile in the active area.

The foregoing general description and the following detailed descriptionare exemplary and explanatory only and are not restrictive of theinvention, as defined in the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

Embodiments are illustrated in the accompanying figures to improveunderstanding of concepts as presented herein.

FIG. 1 includes an illustration of a dried electroactive film having anon-uniform film thickness.

FIG. 2 includes an illustration of a dried electroactive film having asubstantially flat profile.

FIG. 3 includes an illustration of an exemplary electronic device.

FIG. 4 includes a graph of layer thickness from Example 1.

FIG. 5 includes a graph of layer thickness from Example 2.

FIG. 6 includes a graph of layer thickness from Comparative Example A.

Skilled artisans appreciate that objects in the figures are illustratedfor simplicity and clarity and have not necessarily been drawn to scale.For example, the dimensions of some of the objects in the figures may beexaggerated relative to other objects to help to improve understandingof embodiments.

DETAILED DESCRIPTION

Many aspects and embodiments have been described above and are merelyexemplary and not limiting. After reading this specification, skilledartisans appreciate that other aspects and embodiments are possiblewithout departing from the scope of the invention.

Other features and benefits of any one or more of the embodiments willbe apparent from the following detailed description, and from theclaims. The detailed description first addresses Definitions andClarification of Terms followed by the Process, the Electronic Device,and finally Examples.

1. DEFINITIONS AND CLARIFICATION OF TERMS

Before addressing details of embodiments described below, some terms aredefined or clarified.

The term “aperture ratio” is intended to mean a ratio of the area of apixel available for emitting or responding to radiation to the totalarea of the pixel.

The term “charge transport,” when referring to a layer, material,member, or structure is intended to mean such layer, material, member,or structure facilitates migration of such charge through the thicknessof such layer, material, member, or structure with relative efficiencyand small loss of charge. “Hole transport” refers to charge transportfor positive charges. “Electron transport” refers to charge transportfor negative charges. Although light-emitting materials may also havesome charge transport properties, the term “charge transport layer,material, member, or structure” is not intended to include a layer,material, member, or structure whose primary function is light emission.

The term “electroactive” as it refers to a layer or a material, isintended to indicate a layer or material which electronicallyfacilitates the operation of a device. Examples of active materialsinclude, but are not limited to, materials which conduct, inject,transport, or block a charge, where the charge can be either an electronor a hole, or materials which emit radiation or exhibit a change inconcentration of electron-hole pairs when receiving radiation. Examplesof inactive materials include, but are not limited to, planarizationmaterials, insulating materials, and environmental barrier materials.

The term “electronic device” is intended to mean a collection ofcircuits, electronic components, or any combination thereof thatcollectively, when properly electrically connected and supplied with theappropriate potential(s), performs a function. An electronic device maybe included or be part of a system. Examples of an electronic deviceinclude, but are not limited to, a display, a sensor array, a computersystem, an avionics system, an automobile, a cellular phone, otherconsumer or industrial electronic products, or any combination thereof.

The term “guest material” is intended to mean a material, within a layerincluding a host material, that changes the electronic characteristic(s)or the targeted wavelength of radiation emission, reception, orfiltering of the layer compared to the electronic characteristic(s) orthe wavelength of radiation emission, reception, or filtering of thelayer in the absence of such material.

The term “hole injection,” when referring to a layer, material, member,or structure is intended to mean an electrically conductive orsemiconductive material, layer, member or structure that is adjacent toan anode and facilitates electrode function.

The term “host material” is intended to mean a material, usually in theform of a layer, to which a guest material may or may not be added. Thehost material may or may not have electronic characteristic(s) or theability to emit, receive, or filter radiation.

The term “layer” is used interchangeably with the term “film” and refersto a coating covering a desired area. The term is not limited by size.The area can be as large as an entire device or as small as a specificfunctional area such as the actual visual display, or as small as asingle sub-pixel.

The term “liquid composition” is intended to mean a material that isdissolved in a liquid medium to form a solution, dispersed in a liquidmedium to form a dispersion, or suspended in a liquid medium to form asuspension or an emulsion.

The term “liquid medium” is intended to a liquid within a solution,dispersion, suspension, or emulsion. The term “liquid medium” is usedregardless whether one or more solvents are present, and therefore,liquid medium is used as the singular or plural form (i.e., liquidmedia) of the term.

The term “pixel” is intended to mean the smallest complete, repeatingunit of an array. The term “subpixel” is intended to mean a portion of apixel that makes up only a part, but not all, of a pixel. In afull-color display, a full-color pixel can comprise three sub-pixelswith primary colors in red, green and blue spectral regions. Amonochromatic display may include pixels but no subpixels. A sensorarray can include pixels that may or may not include subpixels.

The term “workpiece” is intended to mean a substrate at any particularpoint of a process sequence. Note that the substrate may notsignificantly change during a process sequence, whereas the workpiecesignificantly changes during the process sequence. For example, at abeginning of a process sequence, the substrate and workpiece are thesame. After a layer is formed over the substrate, the substrate has notchanged, but now the workpiece includes the substrate and the layer.

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having” or any other variation thereof, areintended to cover a non-exclusive inclusion. For example, a process,method, article, or apparatus that comprises a list of elements is notnecessarily limited to only those elements but may include otherelements not expressly listed or inherent to such process, method,article, or apparatus. Further, unless expressly stated to the contrary,“or” refers to an inclusive or and not to an exclusive or. For example,a condition A or B is satisfied by any one of the following: A is true(or present) and B is false (or not present), A is false (or notpresent) and B is true (or present), and both A and B are true (orpresent).

Also, use of “a” or “an” are employed to describe elements andcomponents described herein. This is done merely for convenience and togive a general sense of the scope of the invention. This descriptionshould be read to include one or at least one and the singular alsoincludes the plural unless it is obvious that it is meant otherwise.

Group numbers corresponding to columns within the Periodic Table of theelements use the “New Notation” convention as seen in the CRC Handbookof Chemistry and Physics, 81^(st) Edition (2000-2001).

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although methods and materialssimilar or equivalent to those described herein can be used in thepractice or testing of embodiments of the present invention, suitablemethods and materials are described below. All publications, patentapplications, patents, and other references mentioned herein areincorporated by reference in their entirety, unless a particular passageis cited. In case of conflict, the present specification, includingdefinitions, will control. In addition, the materials, methods, andexamples are illustrative only and not intended to be limiting.

To the extent not described herein, many details regarding specificmaterials, processing acts, and circuits are conventional and may befound in textbooks and other sources within the organic light-emittingdiode display, photodetector, photovoltaic, and semiconductive memberarts.

2. THE PROCESS

When layers are formed by liquid deposition processes, the dried filmsfrequently do not have a uniform thickness across the film area. Thiscan be caused by surface non uniformities in the substrate, edgeeffects, differences in evaporation rates across the wet film, etc. Insome embodiments, electroactive materials are applied by liquiddeposition processes onto workpieces having physical containmentstructures, frequently referred to as well structures. The dried filmcan have non-uniform thickness, such as shown in FIG. 1. Substrate 10,which may have additional layers, has a containment structure shown as20 defining opening 30. The dried electroactive film is shown as 40. Thethickness of the film is measured in a direction perpendicular to theplane of the substrate. It can be seen that the thickness at E isconsiderably greater than the thickness at C. Such thicknessnon-uniformity in an electroactive layer can have an adverse effect ondevice performance. In OLEDs, non-uniformity in light-emitting layerscan cause undesirable effects such as color variation, lower efficiency,and lower lifetime.

There is described herein a process for forming an electroactive layer.The process comprises the following steps, in order:

providing a workpiece having at least one active area;

depositing a liquid composition comprising the electroactive materialonto the workpiece in the active area, to form a wet layer;

treating the wet layer on the workpiece at a controlled temperature inthe range of −25° C. to 80° C. and under a vacuum in the range of 10⁻⁶Torr to 1,000 Torr, for a first period of 1-100 minutes, to form apartially dried layer;

heating the partially dried layer to a temperature above 100° C. for asecond period of 1-50 minutes to form a dried layer,

wherein the dried layer has a substantially flat profile in the activearea.

The term “substantially flat” is intended to mean that the layer has athickness variation of no greater than +/−15% over 90% of the layerarea. In some embodiments, the thickness variation is no greater than+/−10% over 90% of the layer area. An electroactive layer having asubstantially flat profile is shown in FIG. 2. As in FIG. 1, substrate10 has a containment structure shown as 20 defining opening 30. Thedeposited electroactive film after drying is shown as 40. The film has asubstantially flat profile with the thickness at E′ being only slightlygreater than the thickness at C′.

The workpiece includes a substrate and any desired intervening layers.In some embodiments, the workpiece is a TFT substrate having a patternedanode layer thereon. In some embodiments, the workpiece additionally hasa liquid containment structure. In some embodiments, the workpieceadditionally has a first electroactive layer, and a second electroactivelayer is deposited on the first electroactive layer according to theprocess described herein.

The workpiece has at least one active area. The active area is thefunctioning area of the device. In some embodiments, the workpiece has amultiplicity of active areas. In some embodiments, the active areascorrespond to pixel or subpixel units.

The electroactive material is deposited onto the workpiece from a liquidcomposition to form a wet layer. Any liquid medium can be used so longas the electroactive material can be dispersed therein to form asubstantially homogeneous solution, dispersion, emulsion or suspension.Aqueous, semi-aqueous and non-aqueous liquid media can be used. Theexact liquid media used will depend upon the electroactive materialused.

In some embodiments, the electroactive material is a hole-injectionmaterial. In some embodiments, the electroactive material is a holetransport material. In some embodiments, the electroactive material is acombination of host material and photoactive guest material.

Any liquid deposition technique can be used, including continuous anddiscontinuous techniques. Continuous deposition techniques, include butare not limited to, spin coating, gravure coating, curtain coating, dipcoating, slot-die coating, spray coating, and continuous nozzle coating.Discontinuous deposition techniques include, but are not limited to, inkjet printing, gravure printing, and screen printing. In someembodiments, the deposition technique is selected from the groupconsisting of ink jet printing and continuous nozzle coating.

The liquid composition is deposited in at least a first portion of theactive area(s) of the workpiece. In some embodiments, the electroactivematerial is a hole injection material or a hole transport material andis deposited in all of the active area(s) of the workpiece. In someembodiments, the liquid composition comprises a photoactive materialassociated with a first color, and is deposited in a first set of activeareas. A second liquid composition comprising a second photoactivematerial associated with a second color, is then deposited in a secondset of active areas. A third liquid composition comprising a thirdphotoactive material associated with a third color, is then deposited ina third set of active areas.

The wet layer is then partially dried. By this it is meant that asubstantial portion, but not all, of the liquid medium is removed. Insome embodiments, greater than 75% by weight of the liquid medium isremoved; in some embodiments, greater than 85% by weight is removed. Insome embodiments, less than 99% by weight of the liquid medium isremoved; in some embodiments, less than 95% by weight is removed. Thispartial drying step takes place under conditions of controlledtemperature, vacuum pressure, and time.

The exact conditions of temperature, pressure and time will depend onthe composition of the liquid medium and liquid interaction with thesubstrate and well material. Appropriate temperature and pressureconditions are chosen to balance drying rate (via vapor pressure andrate of removal) with substrate/liquid interaction. The surface tensionand viscosity of the liquid medium control wetting on the substrate andmust be considered in choosing the appropriate temperature and pressurefor drying.

In some embodiments, the liquid medium comprises at least two liquidcomponents, and at least one component has a boiling point of greaterthan 100° C. In some embodiments, the partial drying step takes place ata temperature in the range of 20° C.-80° C., at a pressure in the rangeof 10⁻² Torr to 10 Torr, for a time of 5-25 minutes. In someembodiments, the partial drying step takes place at a temperature in therange of 30° C.-60° C., at a pressure in the range of 10⁻² to 1 Torr,for a time of 5-15 minutes.

In some embodiments, the liquid medium comprises one or more liquidcomponents, each of which has a boiling point of less than 80° C. Insome embodiments, the partial drying step takes place at a temperaturein the range of −25° C. to 10° C., at a pressure in the range of 1 Torrto 1000 Torr, for a time of 5-25 minutes. In some embodiments, thepartial drying step takes place at a temperature in the range of −10° C.to 0° C., at a pressure in the range of 10 Torr to 100 Torr, for a timeof 5-15 minutes.

In some embodiments, especially when at least one high boiling solventis present in the liquid medium, high vacuum pumps are used in order tomaintain vacuum and prevent saturation with solvent vapor. Examples ofhigh vacuum pumps include dry vacuum pumps, turbo pumps, rotary vanevacuum pumps, oil diffusion pumps, cryogenic pumps, and sorption pumps.In some embodiments, the pressure is maintained at less than 10⁻⁴ Torrwith these pumps. In some embodiments, the pressure is in the range of10⁻⁵ Torr to 10⁻⁶ Torr. In some embodiments, turbomolecular pumps areused. These pumps generally employ multiple states consisting ofrotor/stator pairs mounted in series. In some cases, these pumps work incombination with a backing pump. Such pumps have been reviewed in, forexample, “Vacuum Techniques” (3^(rd) edition), Robert M. Besancon, ed,pp. 1278-1284, Van Nostrand Reinhold, N.Y. (1990).

The workpiece is then heated to a temperature above 100° C. for a secondperiod of 1-50 minutes. In some embodiments, the temperature is in therange of 110° C.-150° and the heating time is in the range of 10-30minutes.

In some embodiments, the liquid composition comprises a photoactivematerial, and three different compositions associated with first,second, and third colors are deposited in first, second and third setsof active areas. In this case, the partial drying and heating steps canbe carried out after the deposition of each color. Alternatively, thethree different colors can be deposited, and then the partial drying andheating steps carried out.

3. ELECTRONIC DEVICE

There is provided an electronic device having at least one active areacomprising an anode, a cathode, and at least one electroactive layertherebetween, wherein the electroactive layer is formed by liquiddeposition and has a substantially flat profile in the active area.

Devices for which the process described herein can be used includeorganic electronic devices. The term “organic electronic device” orsometimes just “electronic device” is intended to mean a deviceincluding one or more organic semiconductor layers or materials. Anorganic electronic device includes, but is not limited to: (1) a devicethat converts electrical energy into radiation (e.g., a light-emittingdiode, light emitting diode display, diode laser, or lighting panel),(2) a device that detects a signal using an electronic process (e.g., aphotodetector, a photoconductive cell, a photoresistor, a photoswitch, aphototransistor, a phototube, an infrared (“IR”) detector, or abiosensors), (3) a device that converts radiation into electrical energy(e.g., a photovoltaic device or solar cell), (4) a device that includesone or more electronic components that include one or more organicsemiconductor layers (e.g., a transistor or diode), or any combinationof devices in items (1) through (4).

As shown in FIG. 3, one embodiment of a device, 100, has an anode layer110, a photoactive layer 140, and a cathode layer 160. The term“photoactive” is intended to mean to any material that exhibitselectroluminescence or photosensitivity. Also shown are three optionallayers: hole injection layer 120; hole transport layer 130; and electroninjection/transport layer 150. At least one of the anode and cathode islight-transmitting so that light can pass through the electrode.

The device may include a support or substrate (not shown) that can beadjacent to the anode layer 110 or the cathode layer 160. Mostfrequently, the support is adjacent the anode layer 110. The support canbe flexible or rigid, organic or inorganic. Examples of supportmaterials include, but are not limited to, glass, ceramic, metal, andplastic films.

The anode layer 110 is an electrode that is more efficient for injectingholes compared to the cathode layer 160. Thus, the anode has a higherwork-function than the cathode. The anode can include materialscontaining a metal, mixed metal, alloy, metal oxide or mixed oxide.Suitable materials include the mixed oxides of the Group 2 elements(i.e., Be, Mg, Ca, Sr, Ba, Ra), the Group 11 elements, the elements inGroups 4, 5, and 6, and the Group 8-10 transition elements. If the anodelayer 110 is to be light transmitting, mixed oxides of Groups 12, 13 and14 elements, such as indium-tin-oxide, may be used. As used herein, thephrase “mixed oxide” refers to oxides having two or more differentcations selected from the Group 2 elements or the Groups 12, 13, or 14elements. Some non-limiting, specific examples of materials for anodelayer 110 include, but are not limited to, indium-tin-oxide (“ITO”),indium-zinc-oxide (“IZO”), aluminum-tin-oxide (“ATO”), gold, silver,copper, and nickel.

In some embodiments, there is a liquid containment pattern, not shown,over the anode. The term “liquid containment pattern” is intended tomean a pattern which serves a principal function of constraining orguiding a liquid within an area or region as it flows over theworkpiece. The liquid containment pattern can be a physical containmentstructure or a chemical containment layer. Physical containmentsstructures can include cathode separators or a well structure. The term“chemical containment layer” is intended to mean a patterned layer thatcontains or restrains the spread of a liquid material by surface energyeffects rather than physical barrier structures. The term “contained”when referring to a layer, is intended to mean that the layer does notspread significantly beyond the area where it is deposited. The term“surface energy” is the energy required to create a unit area of asurface from a material. A characteristic of surface energy is thatliquid materials with a given surface energy will not wet surfaces witha lower surface energy.

The hole injection layer 120 can be formed with polymeric materials,such as polyaniline (PANI) or polyethylenedioxythiophene (PEDOT), whichare often doped with protonic acids. The protonic acids can be, forexample, poly(styrenesulfonic acid),poly(2-acrylamido-2-methyl-1-propanesulfonic acid), and the like. Thehole injection layer 120 can comprise charge transfer compounds, and thelike, such as copper phthalocyanine and thetetrathiafulvalene-tetracyanoquinodimethane system (TTF-TCNQ). In oneembodiment, the hole injection layer 120 is made from a dispersion of aconducting polymer and a colloid-forming polymeric acid. Such materialshave been described in, for example, published U.S. patent applications2004-0102577, 2004-0127637, and 2005-0205860.

In some embodiments, optional hole transport layer 130 is present.between anode layer 110 and photoactive layer 140. In some embodiments,optional hole transport layer is present between a buffer layer 120 andphotoactive layer 140. Examples of hole transport materials have beensummarized for example, in Kirk-Othmer Encyclopedia of ChemicalTechnology, Fourth Edition, Vol. 18, p. 837-860, 1996, by Y. Wang. Bothhole transporting molecules and polymers can be used. Commonly used holetransporting molecules include, but are not limited to:4,4′,4″-tris(N,N-diphenyl-amino)-triphenylamine (TDATA);4,4′,4″-tris(N-3-methylphenyl-N-phenyl-amino)-triphenylamine (MTDATA);N,N′-diphenyl-N,N′-bis(3-methylphenyl)-[1,1′-biphenyl]-4,4′-diamine(TPD); 1,1-bis[(di-4-tolylamino) phenyl]cyclohexane (TAPC);N,N′-bis(4-methylphenyl)-N,N′-bis(4-ethylphenyl)-[1,1′-(3,3′-dimethyl)biphenyl]-4,4′-diamine(ETPD); tetrakis-(3-methylphenyl)-N,N,N′,N′-2,5-phenylenediamine (PDA);α-phenyl-4-N,N-diphenylaminostyrene (TPS); p-(diethylamino)benzaldehydediphenylhydrazone (DEH); triphenylamine (TPA);bis[4-(N,N-diethylamino)-2-methylphenyl](4-methylphenyl)methane (MPMP);1-phenyl-3-[p-(diethylamino)styryl]-5-[p-(diethylamino)phenyl]pyrazoline(PPR or DEASP); 1,2-trans-bis(9H-carbazol-9-yl)cyclobutane (DCZB);N,N,N′,N′-tetrakis(4-methylphenyl)-(1,1′-biphenyl)-4,4′-diamine (TTB);N,N′-bis(naphthalen-1-yl)-N,N′-bis-(phenyl)benzidine (α-NPB); andporphyrinic compounds, such as copper phthalocyanine. Commonly used holetransporting polymers include, but are not limited to,polyvinylcarbazole, (phenylmethyl)polysilane, poly(dioxythiophenes),polyanilines, and polypyrroles. It is also possible to obtain holetransporting polymers by doping hole transporting molecules such asthose mentioned above into polymers such as polystyrene andpolycarbonate.

Depending upon the application of the device, the photoactive layer 140can be a light-emitting layer that is activated by an applied voltage(such as in a light-emitting diode or light-emitting electrochemicalcell), a layer of material that responds to radiant energy and generatesa signal with or without an applied bias voltage (such as in aphotodetector). In one embodiment, the photoactive material is anorganic electroluminescent (“EL”) material. Any EL material can be usedin the devices, including, but not limited to, small molecule organicfluorescent compounds, fluorescent and phosphorescent metal complexes,conjugated polymers, and mixtures thereof. Examples of fluorescentcompounds include, but are not limited to, pyrene, perylene, rubrene,coumarin, derivatives thereof, and mixtures thereof. Examples of metalcomplexes include, but are not limited to, metal chelated oxinoidcompounds, such as tris(8-hydroxyquinolato)aluminum (Alq3);cyclometalated iridium and platinum electroluminescent compounds, suchas complexes of iridium with phenylpyridine, phenylquinoline, orphenylpyrimidine ligands as disclosed in Petrov et al., U.S. Pat. No.6,670,645 and Published PCT Applications WO 03/063555 and WO2004/016710, and organometallic complexes described in, for example,Published PCT Applications WO 03/008424, WO 03/091688, and WO 03/040257,and mixtures thereof. Electroluminescent emissive layers comprising acharge carrying host material and a metal complex have been described byThompson et al., in U.S. Pat. No. 6,303,238, and by Burrows and Thompsonin published PCT applications WO 00/70655 and WO 01/41512. Examples ofconjugated polymers include, but are not limited topoly(phenylenevinylenes), polyfluorenes, poly(spirobifluorenes),polythiophenes, poly(p-phenylenes), copolymers thereof, and mixturesthereof.

Optional layer 150 can function both to facilitate electroninjection/transport, and can also serve as a confinement layer toprevent quenching reactions at layer interfaces. More specifically,layer 150 may promote electron mobility and reduce the likelihood of aquenching reaction if layers 140 and 160 would otherwise be in directcontact. Examples of materials for optional layer 150 include, but arenot limited to, metal chelated oxinoid compounds, including metalquinolate derivatives such as tris(8-hydroxyquinolato)aluminum (AlQ),bis(2-methyl-8-quinolinolato)(p-phenylphenolato) aluminum (BAlq),tetrakis-(8-hydroxyquinolato)hafnium (HfQ) andtetrakis-(8-hydroxyquinolato)zirconium (ZrQ);tetrakis(8-hydroxyquinolinato)zirconium (ZrQ); azole compounds such as2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD),3-(4-biphenylyl)-4-phenyl-5-(4-t-butylphenyl)-1,2,4-triazole (TAZ), and1,3,5-tri(phenyl-2-benzimidazole)benzene (TPBI); quinoxaline derivativessuch as 2,3-bis(4-fluorophenyl)quinoxaline; phenanthroline derivativessuch as 9,10-diphenylphenanthroline (DPA) and2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA); and any one ormore combinations thereof. Alternatively, optional layer 150 may beinorganic and comprise BaO, LiF, Li₂O, CsF, or the like. In someembodiments, two electron transport/injection layers are present. Afirst organic electron transport layer is present adjacent to thephotoactive layer, and a second inorganic electron injection layer ispresent adjacent to the cathode.

The cathode layer 160 is an electrode that is particularly efficient forinjecting electrons or negative charge carriers. The cathode layer 160can be any metal or nonmetal having a lower work function than the anodelayer 110.

Materials for the cathode layer can be selected from alkali metals ofGroup 1 (e.g., Li, Na, K, Rb, Cs,), the Group 2 metals (e.g., Mg, Ca,Ba, or the like), the Group 12 metals, the lanthanides (e.g., Ce, Sm,Eu, or the like), and the actinides (e.g., Th, U, or the like).Materials such as aluminum, indium, yttrium, and combinations thereof,may also be used. Specific non-limiting examples of materials for thecathode layer 160 include, but are not limited to, barium, lithium,cerium, cesium, europium, rubidium, yttrium, magnesium, samarium, andalloys and combinations thereof.

Other layers in the device can be made of any materials which are knownto be useful in such layers upon consideration of the function to beserved by such layers.

In some embodiments, an encapsulation layer (not shown) is depositedover the contact layer 160 to prevent entry of undesirable components,such as water and oxygen, into the device 100. Such components can havea deleterious effect on the organic layer 140. In one embodiment, theencapsulation layer is a barrier layer or film. In one embodiment, theencapsulation layer is a glass lid.

Though not depicted, it is understood that the device 100 may compriseadditional layers. Other layers that are known in the art or otherwisemay be used. In addition, any of the above-described layers may comprisetwo or more sub-layers or may form a laminar structure. Alternatively,some or all of anode layer 110, the buffer layer 120, the hole transportlayer 130, the electron transport layer 150, cathode layer 160, andother layers may be treated, especially surface treated, to increasecharge carrier transport efficiency or other physical properties of thedevices. The choice of materials for each of the component layers ispreferably determined by balancing the goals of providing a device withhigh device efficiency with device operational lifetime considerations,fabrication time and complexity factors and other considerationsappreciated by persons skilled in the art. It will be appreciated thatdetermining optimal components, component configurations, andcompositional identities would be routine to those of ordinary skill ofin the art.

In most cases, the anode 110 and the cathode 160 are formed by achemical or physical vapor deposition process. In some embodiments, theanode layer will be patterned and the cathode will be an overallcontinuous layer.

In some embodiments, the electron transport/injection layer or layersare also formed by a chemical or physical vapor deposition process.

In some embodiments, at least the photoactive layer is formed by liquiddeposition according to the process described herein.

In some embodiments, hole injection and hole transport layers are formedby liquid deposition according to the process described herein.

In one embodiment, the different layers have the following range ofthicknesses: anode 110, 500 Å-5000 Å, in one embodiment 1000 Å-2000 Å;optional buffer layer 120, 50 Å-2000 Å, in one embodiment 200 Å-1000 Å;optional hole transport layer 130, 50 Å-2000 Å, in one embodiment 100Å-1000 Å; photoactive layer 140, 10 Å-2000 Å, in one embodiment 100Å-1000 Å; optional electron transport layer 150, 50 Å-2000 Å, in oneembodiment 100 Å-1000 Å; cathode 160, 200 Å-10000 Å, in one embodiment300 Å-5000 Å. The location of the electron-hole recombination zone inthe device, and thus the emission spectrum of the device, can beaffected by the relative thickness of each layer. Thus the thickness ofthe electron-transport layer should be chosen so that the electron-holerecombination zone is in the light-emitting layer. The desired ratio oflayer thicknesses will depend on the exact nature of the materials used.

In operation, a voltage from an appropriate power supply (not depicted)is applied to the device 100. Current therefore passes across the layersof the device 100. Electrons enter the photoactive layer, releasingphotons. In some OLEDs, called active matrix OLED displays, individualpixels may be independently excited by the passage of current. In someOLEDs, called passive matrix OLED displays, individual pixies may beexcited at the intersections of rows and columns of electrical contactlayers.

Although methods and materials similar or equivalent to those describedherein can be used in the practice or testing of the present invention,suitable methods and materials are described below. All publications,patent applications, patents, and other references mentioned herein areincorporated by reference in their entirety. In case of conflict, thepresent specification, including definitions, will control. In addition,the materials, methods, and examples are illustrative only and notintended to be limiting.

It is to be appreciated that certain features of the invention whichare, for clarity, described above and below in the context of separateembodiments, may also be provided in combination in a single embodiment.Conversely, various features of the invention that are, for brevity,described in the context of a single embodiment, may also be providedseparately or in any subcombination. Further, reference to values statedin ranges include each and every value within that range.

EXAMPLES

The concepts described herein will be further described in the followingexamples, which do not limit the scope of the invention described in theclaims.

Example 1

This example demonstrates the fabrication of an electroactive film forOLED application having a substantially flat profile. The followingmaterials were used:

-   -   anode=Indium Tin Oxide (ITO): 180 nm    -   buffer layer=Buffer 1 (20 nm), which is an aqueous dispersion of        an electrically conductive polymer and a polymeric fluorinated        sulfonic acid. Such materials have been described in, for        example, published U.S. patent applications US 2004/0102577, US        2004/0127637, and US 2005/0205860.    -   hole transport layer=HT-1, which is an arylamine-containing        copolymer. Such materials have been described in, for example,        published U.S. patent application US 2008/0071049.    -   photoactive layer=13:1 host H1:dopant E1. Host H1 is an        anthracene derivative. Such materials have been described in,        for example, U.S. Pat. No. 7,023,013. E1 is an arylamine        compound. Such materials have been described in, for example,        U.S. published patent application US 2006/0033421.    -   electron transport layer=MQ, which is a metal quinolate        derivative cathode=LiF/Al (0.5/100 nm)

OLED devices were fabricated by a combination of solution processing andthermal evaporation techniques. Patterned indium tin oxide (ITO) coatedglass substrates from Thin Film Devices, Inc were used. These ITOsubstrates are based on Corning 1737 glass coated with ITO having asheet resistance of 50 ohms/square and 80% light transmission. A wellpattern was fabricated on the ITO substrate using standardphotolithographic processes. The well was defined by a width of 32microns.

Immediately before device fabrication the cleaned, patterned substrateswere treated with UV ozone for 10 minutes. Immediately after cooling, anaqueous dispersion of Buffer 1 was spin-coated over the ITO surface andheated to remove solvent. After cooling, the substrates were thenspin-coated with a solution of the hole transport material, and thenheated to remove solvent. A chemical containment layer was formed asdescribed in published U.S. patent application US 2007/0205409. Thepattern defined a surface energy well to contain nozzle printedphotoactive inks. The surface energy well was 40 microns wide.

An emissive layer solution was formed by dissolving the host and dopant,described above, in an organic solvent medium, as described in publishedPCT application WO 2007/145979.

The substrates were nozzle printed with the emissive layer solution, andvacuum dried to remove solvent. Immediately after printing, the platewas placed in a vacuum chamber held at 20° C. and pumped to 500 mTorrfor 14 minutes before venting with nitrogen. The plate was then bakedfor 30 minutes at 140° C. on a hotplate.

Film thickness and profile measurements were made on a plate that wasnot made into an OLED device, but was fabricated through the emissivelayer in an identical manner. A KLA-Tencor P-15 stylus profilometer withlow force head was used for thickness/profile measurement. Printedphotoactive layer thickness and profile were determined by subtracting anon-printed line from a printed line in close proximity. This techniqueallows profile differences in under-layers to be de-coupled from theemissive layer. FIG. 4 shows the profile of the printed photoactivelayer with aperture ratio=0.92.

Example 2

This example demonstrates the fabrication of an electroactive film forOLED application having a substantially flat profile using aturbomolecular pump in the drying step. The following materials wereused:

-   -   anode=ITO (180 nm)    -   buffer layer=Buffer 1 (20 nm)    -   hole transport layer=HT-2 (20 nm), which is an        arylamine-containing polymer    -   photoactive layer=13:1 host H1:dopant E2 (40 nm). E2 is an        arylamine compound as described in, for example, U.S. published        patent application US 2006/0033421.    -   electron transport layer=MQ (10 nm)    -   cathode=LiF/Al (0.5/100 nm)

OLED devices were fabricated by a combination of solution processing andthermal evaporation techniques, as described in Example 1, except forthe width of the surface energy well (52 nm) and the drying step afterprinting.

The substrate was nozzle printed with the emissive layer solution, anddried using a turbomolecular pump. Immediately after printing the platewas placed in a vacuum chamber on a substrate held at 20° C. and pumpedto 1×10⁻⁶ Torr. After the high vacuum drying step the plate was placedon a hotplate at 140° C. for 30 min.

Film thickness and profile measurements were made using a KLA-TencorP-15 stylus profilometer with low force head. Printed photoactive layerthickness and profile were determined by subtracting a non-printed linefrom a printed line in close proximity. This technique allows profiledifferences in under-layers to be de-coupled from the emissive layer.FIG. 5 shows the profile of the printed photoactive layer with apertureratio=0.82.

Comparative Example A

OLED devices were fabricated using the same materials as in Example 2.The devices were fabricated using the same procedures as in Example 2,except for the drying step after printing. Immediately after thesubstrates were nozzle printed with the emissive layer solution, theplate was placed on a hotplate at 140° C. for 30 min.

Film thickness and profile measurements were made as in Example 1. FIG.6 shows the profile of the printed photoactive layer, with apertureratio=0.41.

Note that not all of the activities described above in the generaldescription or the examples are required, that a portion of a specificactivity may not be required, and that one or more further activitiesmay be performed in addition to those described. Still further, theorder in which activities are listed are not necessarily the order inwhich they are performed.

In the foregoing specification, the concepts have been described withreference to specific embodiments. However, one of ordinary skill in theart appreciates that various modifications and changes can be madewithout departing from the scope of the invention as set forth in theclaims below. Accordingly, the specification and figures are to beregarded in an illustrative rather than a restrictive sense, and allsuch modifications are intended to be included within the scope ofinvention.

Benefits, other advantages, and solutions to problems have beendescribed above with regard to specific embodiments. However, thebenefits, advantages, solutions to problems, and any feature(s) that maycause any benefit, advantage, or solution to occur or become morepronounced are not to be construed as a critical, required, or essentialfeature of any or all the claims.

It is to be appreciated that certain features are, for clarity,described herein in the context of separate embodiments, may also beprovided in combination in a single embodiment. Conversely, variousfeatures that are, for brevity, described in the context of a singleembodiment, may also be provided separately or in any subcombination.Further, reference to values stated in ranges include each and everyvalue within that range.

What is claimed is:
 1. A process for forming a layer of electroactivematerial, comprises: providing a workpiece having at least one activearea; depositing a liquid composition comprising the electroactivematerial onto the workpiece in the active area, to form a wet layer;treating the wet layer on the workpiece at a controlled temperature inthe range of −25 to 80° C. and under a vacuum in the range of 10⁻⁶ to1,000 Torr, for a first period of 1-100 minutes, to form a partiallydried layer; heating the partially dried layer to a temperature above100° C. for a second period of 1-50 minutes to form a dried layer,wherein the dried layer has a substantially flat profile in the activearea.
 2. The process of claim 1, wherein the dried layer has a thicknessvariation of less than +/−10% over 90% of the active area.
 3. Theprocess of claim 1, wherein the liquid composition is deposited by atechnique selected from the group consisting of ink jet printing andcontinuous nozzle coating.
 4. The process of claim 1, wherein theworkpiece has a multiplicity of active areas.
 5. The process of claim 4,wherein the electroactive material comprises a host material and aphotoactive guest material corresponding to a first color, and theliquid composition is deposited in a first portion of the active areas.6. The process of claim 5, wherein a second liquid compositioncomprising a second host material and a second photoactive guestmaterial corresponding to a second color is deposited in a secondportion of the active areas.
 7. The process of claim 6, wherein a thirdliquid composition comprising a third host material and a thirdphotoactive guest material corresponding to a third color is depositedin a third portion of the active areas.
 8. The process of claim 1,wherein the electroactive material consists essentially of a holeinjection material.
 9. The process of claim 1, wherein the electroactivematerial consists essentially of a hole transport material.
 10. Theprocess of claim 1, wherein the wet layer on the workpiece is treated ata temperature in the range of 20-80° C., at a pressure in the range of10⁻² to 10 Torr, for a time of 5-25 minutes.
 11. The process of claim 1,wherein the wet layer on the workpiece is treated at a temperature inthe range of 30-60° C., at a pressure in the range of 10⁻² to 1 Torr,for a time of 5-15 minutes.
 12. The process of claim 1, wherein the wetlayer on the workpiece is treated at a temperature in the range of −25to 10° C., at a pressure in the range of 1 to 1000 Torr, for a time of5-25 minutes.
 13. The process of claim 1, wherein the wet layer on theworkpiece is treated at a temperature in the range of −10 to 0° C., at apressure in the range of 10 to 100 Torr, for a time of 5-15 minutes. 14.The process of claim 1, wherein the vacuum is in the range of 10⁻⁴ to10⁻⁶ Torr.
 15. The process of claim 14, wherein the vacuum is applied bymeans of a pump selected from the group consisting of dry vacuum pumps,turbo pumps, rotary vane vacuum pumps, oil diffusion pumps, cryogenicpumps, and sorption pumps.
 16. The process of claim 15, wherein the pumpis a turbomolecular pump.
 17. An electronic device having at least oneactive area comprising an anode, a cathode, and an electroactive layertherebetween, wherein the electroactive layer is formed by liquiddeposition and has a substantially flat profile.
 18. The device of claim17, wherein the electroactive layer is a photoactive layer.
 19. Thedevice of claim 18, wherein the electroactive layer is a light-emittinglayer.
 20. The device of claim 17, wherein the electroactive layer is ahole transport layer.
 21. The device of claim 17, wherein theelectroactive layer is a hole injection layer.
 22. The device of claim17, wherein the active area is divided into subpixel areas by a physicalcontainment structure, and the electroactive layer is in the subpixelareas.